JP3956501B2 - Method for dyeing polyamide fiber and dyed product thereof - Google Patents

Description

【化２】

【化３】

（式中において、Ｚは−ＣＨ＝ＣＨ₂ 又は −ＣＨ₂ ＣＨ₂ Ｚ¹ を表しＺ¹ は−ＯＳＯ₃ Ｈ、−ＯＣＯＣＨ₃ 、−ＯＰＯ₃ Ｈ₂ 、−Ｃｌ、などの脱離基を示す）
【化４】

（式中において、Ｘ₁ 〜Ｘ₃ はＣｌまたはＦ）
【化５】

こういった反応基を持つ染料としてはたとえばＳｕｍｉｆｉｘ、Ｓｕｍｉｆｉｘ Ｓｕｐｒａ、Ｒｅｍａｚｏｌ、Ｃｅｌｍａｚｏｌ、Ｌｅｖａｆｉｘ、Ｐｒｏｃｉｏｎ、Ｃｉｂａｃｒｏｎ、Ｂａｓｉｌｅｎ、Ｄｒｉｍａｒｅｎｅ、Ｄｒｉｍａｌａｎ、Ｌａｎａｓｏｌ、Ｋａｙａｃｉｏｎ、Ｍｉｋａｃｉｏｎ、ＫａｙａｃｅｒｏｎＲｅａｃｔ、Ｖｅｒｏｆｉｘ、Ｒｅａｌａｎ等の冠称名で市販されているものを用いることができる。いずれの反応染料も本発明に適用できるが、特に式[III]に示すスルファトエチルスルホン基等の保護基により活性反応基が保護されている反応基のみを有する染料を本発明に適用する場合、十分な固着量と湿潤堅牢性を得るには保護基を外して反応基を活性化させる必要がある。これらの保護基を完全に脱離させるためにはアルカリが必要である場合が多く、アルカリによる脱保護が必要な染料を使用する場合染色前のアルカリ前処理が必要になる。この観点から本発明においては、簡便性、再現性に優れる、ブロモアクリルアミド基、モノクロロトリアジン基、モノフルオロトリアジン基、カルボキシピリジニオトリアジン基、フルオロクロロピリミジン基のうち少なくとも１つ以上を有する反応染料により染色したときが、均染性と堅牢度を向上させることができるのである。これらの反応基を１つ以上有していれば、その他の反応基は、例えばビニルスルホン基やスルファトエチルスルホン基との異種多官能基型であってもよい。これらの染料は、市販されているものを適宜使用することができ、例えばＳｕｍｉｆｉｘＳｕｐｒａ染料（住友化学（株）製）、Ｃｉｂａｃｒｏｎ染料（チバスペシャリティケミカルズ（株）製）、Ｌａｎａｓｏｌ染料（チバスペシャリティケミカルズ（株）製）、Ｐｒｏｃｉｏｎ染料（三井ＢＡＳＦ染料（株）製）、Ｋａｙａｃｉｏｎ染料（日本化薬（株）製）、ＫａｙａｃｅｒｏｎＲｅａｃｔ染料（日本化薬（株）製）、Ｂａｓｉｌｅｎ染料（三井ＢＡＳＦ（株）製）、Ｄｒｉｍａｌａｎ Ｆ染料（クラリアント（株）製）、Ｄｒｉｍａｒｅｎｅ染料（クラリアント（株）製）、Ｒｅａｌａｎ染料（ダイスター（株）製）などを使用することができる。
【００１７】
本発明では浸染、捺染、パディング染色等の染色方法を適用することができ、捺染やパディング染色の場合は反応染料と糊剤（好ましくは染料の非反応性の水溶性高分子）で染液を調整し、適宜硫酸アンモニウムや酒石酸アンモニウム等公知のｐＨ調整剤、還元防止剤、堅牢度向上剤等を添加する。この染液を布帛に捺染又はパディングし、８０℃〜１３０℃で１０〜３０分程度飽和又は過熱蒸気による湿熱処理、乾熱処理、マイクロ波照射などを行い染色する。
【００１８】
本発明においては、特に浸染が好ましく適用される。浸染の場合、染液のｐＨは、吸尽率を向上させつつ染色物の堅牢度低下を防ぐために３以上とすることが好ましく、染料の吸尽率・利用率を低下させることなく濃色を表現できるようにするために８以下とすることが好ましい。またこの範囲とすることは排水負荷や経済性の点からも好適である。より好ましくは４以上７以下に、さらに好ましくは４以上６以下に調整する。
【００１９】
かかるｐＨ調整には、酸または緩衝液を適宜調製して行う。ここで使用する酸や塩等は特に限定されず、酸発生剤としては酢酸、蟻酸、塩酸等を使用することができ、緩衝液としては、酢酸と酢酸ナトリウムにより調製されたもの等を使用することができる。また染料と水以外になにも添加しなくても前記ｐＨが達成されていれば、本発明の効果を達成することができる。
【００２０】
本発明では、均染性、再現性を得るために、均染剤を染液に添加することが好ましく採用される。均染剤には、通常の繊維親和性均染剤及び／又は染料親和性の均染剤を使用することができる。例えばアニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤等の界面活性剤や芒硝等の無機塩など種々の物を使用することができる。 本発明の染色法においては、染料に親和性を持つ界面活性剤が好ましく、特に分子構造中に３級化及び／又は４級化された窒素原子を含む界面活性剤が好ましく、さらに好ましくはさらにアニオン性基を含む両性界面活性剤が好ましく用いられる。これらを使用した場合の方が染色物の堅牢度及び／又は均染性が向上するため好ましい。両性界面活性剤としてはカルボン酸塩型のアミノ酸型やベタイン型、スルホン酸塩型等を使用することができるが、本発明においてはスルホン酸塩型及び／又はアミノ酸型、特にアミノ酸型及び／又はその類似型、つまりアルキルアミンのカルボン酸及び／又はその半エステル化合物等の界面活性剤がより好ましく用いられる。例えばアルコキシ脂肪酸アミンのマレイン酸又はフタル酸の半エステル化合物を使用することができるが、その４級アンモニウム化合物等でもよい。かかる界面活性剤の添加量は使用する染料の種類、分子量、添加量（濃度）により異なるが、好ましくは０．５％〜８％ｏｗｆ、さらに好ましくは１〜５％ｏｗｆ添加する。
【００２１】
またさらに両性界面活性剤の他にアニオン性界面活性剤やノニオン界面活性剤、カチオン性界面活性剤、無機塩類などを併用して用いることもできる。好ましくは分子構造中に３級化及び／又は４級化された窒素原子を含む両性界面活性剤及び／又はカチオン性界面活性剤とアニオン性界面活性剤を併用して用いることで均染性は向上する。
【００２２】
本発明においては、反応染料で染色した後、酸性染料で染色した場合と同様にタンニン酸などを使用してフィックス処理を施すことも可能であるが、より柔軟な風合いを保ち、高堅牢性を得るためには、未固着染料を除くソーピング処理を施すことが好ましい。かかるソーピング処理とは、染色後に未固着染料あるいは弱い結合力で染着している脱落しやすい染料を取り除く処理のことをいい、一部の未固着染料や弱い結合力で染着している染料を繊維内に封じ込めるフィックス処理とは異なるものである。ソーピング処理は、湿潤堅牢度をよくする観点からｐＨ６以上とすることが好ましく、変色を防止するためｐＨ１３以下とすることが好ましい。より好ましくはｐＨ８〜１２の範囲がより未固着染料を除去することができ堅牢度が向上するため好ましい。上記ｐＨによって調整された液に界面活性剤等を適宜添加することが洗浄効果を向上させるために好ましい。界面活性剤としては特に限定されず、例えばアニオン性界面活性剤、ノニオン性界面活性剤、又はその配合品などを用いることが出来る。
【００２３】
本発明により得られる染色布帛は、染料が繊維に強固に染着反応しているため、例えばピリジン２０％水溶液等で１００℃において連続的に６時間程度処理しても、繊維構造物の色が残るものである。従来の酸性染料で染色された物にこういった処理をした場合、大部分の染料が脱落してわずかに色が確認される程度かあるいは染色前の状態になる。
【００２４】
また本発明のかかる方法によって染色された染色物は、色相が鮮明で風合いの硬化なく、湿潤堅牢なポリアミド系繊維構造物である。さらに、２種以上のポリアミドからなる繊維、例えば共重合ポリアミドと通常のホモポリマーからなるポリアミド、特に共重合ポリアミド系繊維とナイロン６及び／又はナイロン６６、あるいは共重合比又は共重合成分の異なる２種以上の共重合ポリアミドを複合した糸若しくは混繊した糸又はそれらの糸を交織したものが反応染料により染色されてなる場合は、ＪＩＳＬ−０８４４ Ａ−２法に定められる洗濯堅牢度が４級以上であり、かつ濃淡異色性を有するものとなる。ここで、濃淡異色性とはポリマー組成の異なる各繊維間に微細な濃淡差および／または色相差がある新規な外観であり、前記した本発明の染色方法により得ることが出来る。これは従来の酸性染料などによる染色方法では得られない効果であり、堅牢性の向上とともに本発明での特徴である。このような外観を得るためには、使用する反応染料が少なくとも、ブロモアクリルアミド基、モノクロロトリアジン基、モノフルオロトリアジン基、カルボキシピリジニオトリアジン基、フルオロクロロピリミジン基を１つ以上有するものである。特に濃淡異色性を大きく生じさせるためには、さらに好ましくはモノクロロトリアジン基、モノフルオロトリアジン基、カルボキシピリジニオトリアジン基から選ばれる少なくとも１つ以上を有する反応染料を使用することが好ましい。
【００２５】
本発明に係る染色物は、カジュアル、スポーツ用途など湿潤堅牢性の要求される分野に特に好ましく用いることができる。
【００２６】
【実施例】
実施例で使用した布帛、染色条件および後処理条件は下記に示すとおりである。また実施例中の洗濯堅牢度は、ＪＩＳ Ｌ−０８４４ Ａ−２法により行い９ファイバーにて汚染を判定した。なお、実施例中の％ｏｗｆは繊維重量に対する重量％を示す。
【００２７】
布帛
布帛ａ ナイロン６糸（７０デニール３６フィラメント）１００％からなる織物
布帛ｂ ナイロン６（８０重量％）にナイロン６６を２０重量％共重合させた共重合ナイロン糸（７０デニール３６フィラメント）からなる織物
染色条件
染料 １％ｏｗｆ
両性界面活性剤 ２％ｏｗｆ
アルベガールＢ（チバスペシャリティケミカルズ（株）製）
ｐＨ ４．８（酢酸／酢酸ナトリウム緩衝液）
浴比 １：２０
温度 ９０℃
時間 ４０分
ソーピング処理条件
グランアップＩＮＡ−５（三洋化成（株）製） ２ｇ／Ｌ
炭酸名ナトリウム ２ｇ／Ｌ
温度 ８０℃
時間 ２０分
フィックス処理条件
ナイロンフィックス５０１（センカ（株）製） ２％ｏｗｆ
温度 ８０℃
時間 ２０分
【００３４】
比較例１
下記染料を用い布帛ａ，ｂを染色、フィックス処理をして染色布帛１（布帛ａ：比較例）、２（布帛ｂ：比較例）を得た。この染色布帛の洗濯堅牢度を評価したところ、ナイロン６からなる染色布帛１の堅牢度は変退色４級、汚染４級であり、良好な染色布帛が得られたが、共重合ナイロンからなる染色布帛２の堅牢度は変退色２級、汚染１〜２級となり非常に悪いことが判った。
【００３５】
ミリング酸性染料
Ｎｙｌｏｓａｎ Ｂｌｕｅ Ｎ−ＧＦＬ（クラリアントジャパン（株）製）
以上の結果から、通常のホモポリマーからなる布帛の堅牢性は酸性染料でも優れているが、共重合ナイロン布帛では、堅牢性の差が大きく現れ、共重合ポリアミドに対し本発明は効果が顕著であることが判る。
【００３６】
実施例１
ナイロン６（３６デニール１７フィラメント）とナイロン６（８０重量％）にナイロン６６が２０重量％共重合された共重合ナイロン（３６デニール１７フィラメント）を１：１で混繊して７０デニール３４フィラメントの混繊糸とし、これにより得られた布帛を、下記染料で染色、ソーピング処理をし染色布帛３を得た。ここで得られた布帛の外観は微細な濃淡差のある新規な外観を呈し、また洗濯堅牢度を評価したところ、変退色４〜５級、汚染４〜５級となり良好な堅牢性であることが判った。
【００３７】
カルボキシピリジニオトリアジン型反応染料
Ｋａｙａｃｅｒｏｎ Ｒｅａｃｔ Ｂｌｕｅ ＣＮ−ＭＧ（日本化薬（株）製）
【００３８】
実施例２
実施例１と同様の布帛、方法で染料を下記に変えて行い、染色布帛４を得た。ここで得られた布帛の外観は染色布帛３より若干濃淡差が小さいものの、穏やかな濃淡差のある新規な外観を呈し、また洗濯堅牢度を評価したところ、変退色４〜５級、汚染４〜５級となり良好な堅牢性であることが判った。
【００３９】
ブロモアクリルアミド型反応染料
Ｌａｎａｓｏｌ Ｂｌｕｅ ３Ｇ（チバスペシャリティケミカルズ（株）製）
【００４０】
比較例２
実施例１と同じ布帛を用い、下記染料で染色しフィックス処理を行って染色布帛５を得た。ここで得られた布帛は微細な濃淡差もなく、また洗濯堅牢度を評価したところ、変退色３級、汚染２〜３級となり、非常に悪いことが判った。
【００４１】
ミリング酸性染料
Ｎｙｌｏｓａｎ Ｂｌｕｅ Ｎ−ＧＦＬ（クラリアントジャパン（株）製）
以上の結果から、共重合ポリアミドとホモポリマーからなるポリアミドの混繊糸を染色することにより、本発明の方法では洗濯堅牢性が良好で、かつ微細な濃淡差を有する新規な外観を有しているのに対し、酸性染料による染色物は洗濯堅牢性も悪く、また外観も微細な濃淡差を得ることが出来ないことが判った。
【００４２】
【発明の効果】
本発明によれば、良好な湿潤堅牢性を有し、また２種以上のポリアミド系繊維を使用することで穏やかな濃淡差のある新規な外観を呈する共重合ポリアミド系繊維染色物を得ることが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for dyeing a copolymerized polyamide fiber excellent in wet fastness and a dyed product thereof.
[0002]
[Prior art]
Conventionally, polyamide fibers made of a homopolymer (for example, nylon 6 fiber or nylon 66 fiber) have been dyed with an acid dye or a metal complex dye and then subjected to a fix treatment. As the development of dyes and fixing agents progresses, the fastness of the dyed products obtained has been remarkably improved. At present, the fastness to washing of the dyed products dyed by these dyes can withstand practical use.
[0003]
In addition to acid dyes and metal complex hydrochloric acid dyes that are conventionally used as dyes that are dyeable to polyamide, disperse dyes, acid mordant dyes, reactive dyes, and the like are known. However, with polyamide fibers made of ordinary homopolymers, there is almost no difference in washing fastness compared to acid dyes, and there is a case where it is rather lowered, so there is no advantage in dyeing with reactive dyes. The fact is that it is rarely used.
[0004]
On the other hand, the fibers made of homopolymers have advantages and disadvantages, for example, nylon 6 has better color development than nylon 66 and is particularly preferably used for clothing. On the other hand, nylon 66 has better heat resistance. . Thus, in order to combine the advantages of the homopolymer or to compensate for the drawbacks, attempts have been made to copolymerize the copolymer components. For example, in Japanese Patent Laid-Open No. 9-512866, nylon 66 is copolymerized to reduce the dyeing speed of nylon 6, and in Japanese Patent Laid-Open No. 8-260241, nylon 6 is used to improve the dyeability of nylon 66. Are copolymerized. Such copolymerization has improved the properties of polyamide fibers made of homopolymers.
[0005]
However, when dyeing fastness, especially washing fastness was evaluated, all of these copolymerized polyamide fibers tended to decrease. Therefore, to compensate for this decrease in fastness, the copolymerization component ratio must be lowered to a level where there is no problem in practical fastness, and as a result, the characteristics to be obtained by copolymerization cannot be fully utilized. There was a problem.
[0006]
[Problems to be solved by the invention]
In view of the background of such prior art, the present invention provides a method for dyeing copolymerized polyamide fibers having good wet fastness and a dyed product thereof.
[0007]
[Means for Solving the Problems]
The present invention employs the following means in order to solve such problems.
[0008]
That is, the dyeing method of the present invention comprises a copolymerized polyamide obtained by copolymerizing at least one or more copolymerization components with respect to the main component polyamide in an amount of 3% by weight or more and less than 60% by weight , and nylon 6 and / or nylon 66. Polyamide fiber made by combining, mixing or interweaving with a reactive dye having at least one bromoacrylamide group, monochlorotriazine group, monofluorotriazine group, carboxypyridiniotriazine group, or fluorochloropyrimidine group To do.
[0009]
And the one aspect | mode of the polyamide-type fiber dyeing | staining of this invention is a polyamide-type dyeing | staining obtained by the said method. Another aspect of the polyamide-based fiber dyed product of the present invention is a copolymerized polyamide-based fiber in which at least one copolymer component is copolymerized in an amount of 3% by weight or more and less than 60% by weight with respect to the main component polyamide. The structure is dyed with a reactive dye containing at least one bromoacrylamide group, monochlorotriazine group, monofluorotriazine group, carboxypyridiniotriazine group, or fluorochloropyrimidine group, and is defined in JIS L-0844 A-2 method. der washfastness quaternary or higher is, and is shall such a shading unique properties.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the copolymerized polyamide fiber is a polyamide fiber in which at least one copolymer component is copolymerized in an amount of 3% by weight or more and less than 60% by weight with respect to the main component polyamide. Here, the main component polyamide refers to the most abundant component among the polyamide components composed of two or more types. The main component polyamide is preferably nylon 6 or nylon 66 from the viewpoint of fastness. When the copolymerization component is less than 3%, there is no difference in fastness from conventional dyeing methods using acid dyes or metal complex dyes. The dyeing method of the present invention is useful for polyamide fibers having a copolymerization component of 3% or more and 60% or less, preferably 5% or more and 50% or less, more preferably 7% or more and 35% or less. It is a particularly useful staining method.
[0011]
The copolymer component is not particularly limited as long as it is a different monomer copolymerizable with the main component polyamide. For example, in the case of a polyamide fiber mainly composed of nylon 66, nylon 4, nylon 6, nylon 610, nylon 12, nylon 6I (hexamethylenediamine and isophthalic acid), nylon 6T (hexamethylenediamine and terephthalic acid) are used as copolymerization components. ) And the like. Among these, a monomer of nylon 6 (ε-caprolactam) is preferable because it is excellent in yarn production stability and hardly causes defects in dyeing. For example, in the case of a polyamide-based fiber having nylon 6 as a main component, monomers such as nylon 4, nylon 66, nylon 610, nylon 12, nylon 6I, nylon 6T and the like are listed as copolymerization components. (Condensate composed of hexamethylenediamine and adipic acid) is preferable because it has excellent yarn-making stability and hardly causes defects in dyeing.
[0012]
The polyamide fiber used in the present invention includes, in addition to the above-mentioned copolymerized polyamide fiber, a yarn or a mixed yarn of a bimetallic type, a core-sheath type or the like with a polyamide made of a normal homopolymer. In dyeing, polyamide fibers made of ordinary homopolymer may be woven with copolymerized polyamide fibers . Also, polyester, acrylic, other synthetic fibers such as polyurethane, wool, silk, natural fibers such as cellulose, rayon, etc. a composite semi-synthetic fibers such as Tencel, may be contained in the form of such commingled or interwoven .
[0013]
The form of the polyamide-based fiber used in the dyeing method of the present invention may be yarn, woven fabric, knitted fabric, non-woven fabric, artificial leather or the like, and further coated with a synthetic polymer such as polyester, acrylic or polyurethane. Alternatively, it may be applied by impregnation.
[0014]
As a reactive dye for use in the present invention is a dye having a reactive group with a covalent bond property to generally hydroxyl group or an amino group is, for example monochlorotriazine group represented by the formula [I] (X = Cl, Y = substituted Group), monofluorotriazine group (X = F, Y = substituent), carboxypyridiniotriazine group (X = formula [II], Y = substituent), dichlorotriazine group (X = Y = Cl), etc. It has at least one known reactive group such as a bromoacrylamide group represented by the formula [V] such as a vinylsulfone group represented by the formula [III], a sulfatoethylsulfone group, a fluorochloropyrimidine group represented by the formula [IV], etc. Ru dye der.
[0015]
These reactive groups Ri dyes der having one or more, such as those of the formula and the same type polyfunctional type reactive dye having two or more monochlorotriazine groups in the molecule of [I], formula [I] A monofunctional trifunctional reactive dye containing the monochlorotriazine group or monofluorotriazine group of formula (III) and the sulfatoethylsulfone group of formula [III] in the same molecule may be used. For example, in formula [I], Y may contain formula [III].
[0016]
[Chemical 1]

[Chemical 2]

[Chemical 3]

(In the formula, Z represents —CH═CH ₂ or —CH ₂ CH ₂ Z ^1, and Z ¹ represents a leaving group such as —OSO ₃ H, —OCOCH ₃ , —OPO ₃ H ₂ , —Cl, etc. )
[Formula 4]

(Wherein X _{1 to} X ₃ are Cl or F)
[Chemical formula 5]

Examples of dyes having such a reactive group include Sumifix, Sumifix Supra, Remazol, Celmazol, Levafix, Procion, Cibacron, Basilen, Dreamarene, Dreamana, Lanacol, Kayacion, and Miacion. Can be used. Any reactive dye can be applied to the present invention. Particularly, a dye having only a reactive group in which an active reactive group is protected by a protective group such as a sulfatoethylsulfone group represented by the formula [III] is applied to the present invention. In order to obtain a sufficient fixing amount and wet fastness, it is necessary to remove the protecting group and activate the reactive group. In order to completely remove these protecting groups, an alkali is often required, and when a dye that requires deprotection with an alkali is used, an alkali pretreatment prior to dyeing is required. In the present invention In this respect, the simplicity, excellent reproducibility, blanking Romo acrylamide groups, monochlorotriazine groups, monofluorotriazine groups, carboxy pyridinium niobium triazine group, the reaction with at least one or more of fluoro chloro pyrimidine group when stained with the dye, there can be improved the levelness and fastness. As long as it has one or more of these reactive groups, the other reactive groups may be of a different polyfunctional group type, such as a vinyl sulfone group or a sulfatoethyl sulfone group. As these dyes, commercially available dyes can be used as appropriate. For example, Sumifix Supra dye (manufactured by Sumitomo Chemical Co., Ltd.), Cibacron dye (manufactured by Ciba Specialty Chemicals Co., Ltd.), Lanasol dye (Ciba Specialty Chemicals Co., Ltd.). )), Procion dye (made by Mitsui BASF dye), Kayacion dye (made by Nippon Kayaku Co., Ltd.), Kayaceron React dye (made by Nippon Kayaku Co., Ltd.), Basilen dye (made by Mitsui BASF Co., Ltd.) , Drimalan F dye (manufactured by Clariant Co., Ltd.), Drimarene dye (manufactured by Clariant Co., Ltd.), Realan dye (manufactured by Dystar Co., Ltd.), and the like can be used.
[0017]
In the present invention, dyeing methods such as dip dyeing, textile printing, and padding dyeing can be applied. In the case of textile printing or padding dyeing, a dye solution is formed with a reactive dye and a paste (preferably a non-reactive water-soluble polymer of the dye). It adjusts and adds well-known pH adjusters, such as ammonium sulfate and ammonium tartrate, a reduction inhibitor, a fastness improving agent, etc. suitably. The dyeing solution is printed or padded on a fabric and dyed by performing wet heat treatment, dry heat treatment, microwave irradiation, or the like with a saturated or superheated steam at 80 ° C. to 130 ° C. for about 10 to 30 minutes.
[0018]
In the present invention, dip dyeing is particularly preferably applied. In the case of dip dyeing, the pH of the dyeing solution is preferably 3 or more in order to improve the exhaustion rate and prevent the fastness of the dyed product from being lowered, and a dark color can be obtained without reducing the exhaustion rate / utilization rate of the dye. In order to be able to express, it is preferably 8 or less. Moreover, it is suitable from the point of drainage load and economical efficiency to set it as this range. More preferably, it is adjusted to 4 or more and 7 or less, and more preferably 4 or more and 6 or less.
[0019]
Such pH adjustment is performed by appropriately preparing an acid or a buffer solution. The acid or salt used here is not particularly limited, and as the acid generator, acetic acid, formic acid, hydrochloric acid or the like can be used, and as the buffer solution, those prepared with acetic acid and sodium acetate are used. be able to. The effect of the present invention can be achieved if the pH is achieved without adding anything other than dye and water.
[0020]
In the present invention, it is preferable to add a leveling agent to the dyeing solution in order to obtain leveling and reproducibility. As the leveling agent, a normal fiber affinity leveling agent and / or a dye affinity leveling agent can be used. For example, various substances such as surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and inorganic salts such as mirabilite can be used. In the dyeing method of the present invention, a surfactant having an affinity for a dye is preferable, and a surfactant containing a nitrogen atom that is tertiary and / or quaternized in the molecular structure is particularly preferable, and further preferably Amphoteric surfactants containing an anionic group are preferably used. The use of these is preferred because the fastness and / or levelness of the dyed product are improved. As the amphoteric surfactant, a carboxylate type amino acid type, betaine type, sulfonate type and the like can be used. In the present invention, sulfonate type and / or amino acid type, particularly amino acid type and / or A surfactant of the similar type, that is, a carboxylic acid of alkylamine and / or a half ester compound thereof is more preferably used. For example, a half-ester compound of maleic acid or phthalic acid of an alkoxy fatty acid amine can be used, but a quaternary ammonium compound thereof may be used. The amount of the surfactant to be added varies depending on the type, molecular weight, and amount (concentration) of the dye used, but is preferably 0.5% to 8% owf, more preferably 1 to 5% owf.
[0021]
In addition to amphoteric surfactants, anionic surfactants, nonionic surfactants, cationic surfactants, inorganic salts and the like can be used in combination. Preferably, the leveling property is improved by using an amphoteric surfactant and / or a cationic surfactant and an anionic surfactant that contain a tertiary and / or quaternized nitrogen atom in the molecular structure. improves.
[0022]
In the present invention, after dyeing with a reactive dye, it is possible to apply a fix treatment using tannic acid as in the case of dyeing with an acid dye, but it maintains a more flexible texture and has high fastness. In order to obtain, it is preferable to perform the soaping process except an unfixed dye. Such soaping treatment refers to a process of removing unfixed dyes or dyes that are easily dyed with weak binding strength after dyeing, and some unfixed dyes or dyes that have been stained with weak binding strength. This is different from the fixing process in which the fiber is contained in the fiber. The soaping treatment is preferably pH 6 or more from the viewpoint of improving wet fastness, and is preferably pH 13 or less in order to prevent discoloration. More preferably, the range of pH 8 to 12 is preferable because unfixed dye can be removed more and fastness is improved. In order to improve the cleaning effect, it is preferable to appropriately add a surfactant or the like to the liquid adjusted by the pH. The surfactant is not particularly limited, and for example, an anionic surfactant, a nonionic surfactant, or a combination thereof can be used.
[0023]
In the dyed fabric obtained by the present invention, since the dye is strongly dyed to the fiber, the color of the fiber structure does not change even if it is continuously treated with a 20% aqueous pyridine solution at 100 ° C. for about 6 hours. It remains. When such a treatment is applied to an object dyed with a conventional acid dye, most of the dye is removed and the color is slightly confirmed or is in a state before dyeing.
[0024]
Further, the dyed product dyed by such a method of the present invention is a polyamide fiber structure having a clear hue and no hardened texture, and is moist and fast. In addition, fibers made of two or more polyamides, different example of copolyamide with a polyamide composed of ordinary homopolymers, in particular copolyamide fibers and nylon 6 and / or nylon 66 or copolymerization ratio or copolymer components, When a yarn composed of two or more types of copolymerized polyamide or a mixed yarn or a combination of these yarns is dyed with a reactive dye, the fastness to washing specified in JIS L-0844 A-2 method is 4 It is a grade or higher and has a light and dark color difference. Here, the light / dark color difference is a novel appearance having a fine light / dark difference and / or hue difference between fibers having different polymer compositions, and can be obtained by the dyeing method of the present invention described above. This is an effect that cannot be obtained by a conventional dyeing method using an acid dye or the like, and is a feature of the present invention as well as improved fastness. In order to obtain such appearance, at least a reactive dye to be used, Ru der having bromo acrylamide groups, monochlorotriazine groups, monofluorotriazine groups, carboxy pyridinium niobium triazine group, a fluoro chloropyrimidine group one or more . In particular, it is preferable to use a reactive dye having at least one or more selected from a monochlorotriazine group, a monofluorotriazine group, and a carboxypyridiniotriazine group in order to produce a large difference in color density.
[0025]
The dyed product according to the present invention can be particularly preferably used in fields requiring wet fastness such as casual use and sports use.
[0026]
【Example】
The fabrics used in the examples, the dyeing conditions, and the post-treatment conditions are as shown below. In addition, the fastness to washing in the examples was determined according to JIS L-0844 A-2 method, and contamination was determined with 9 fibers. In addition,% owf in an Example shows weight% with respect to fiber weight.
[0027]
Fabric fabric a Fabric fabric consisting of 100% nylon 6 yarn (70 denier 36 filament) b Fabric fabric consisting of copolymer nylon yarn (70 denier 36 filament) in which nylon 6 (80 wt%) is copolymerized with 20 wt% nylon 66 Dyeing condition dye 1% owf
Amphoteric surfactant 2% owf
Albegal B (Ciba Specialty Chemicals Co., Ltd.)
pH 4.8 (acetic acid / sodium acetate buffer)
Bath ratio 1:20
Temperature 90 ° C
Time 40 minutes soaping treatment condition Grand Up INA-5 (manufactured by Sanyo Chemical Co., Ltd.) 2g / L
Sodium carbonate name 2g / L
80 ℃
Time 20 minutes Fix processing condition Nylon Fix 501 (Senka Co., Ltd.) 2% owf
80 ℃
Time 20 minutes 【0034】
Comparative Example 1
Fabrics a and b were dyed and fixed using the following dyes to obtain dyed fabrics 1 (fabric a: comparative example) and 2 (fabric b: comparative example). When the fastness to washing of this dyed fabric was evaluated, the fastness of dyed fabric 1 made of nylon 6 was grade 4 discoloration and grade 4 of contamination, and a good dyed fabric was obtained. It was found that the fastness of the fabric 2 was very bad with a discoloration grade of 2 and a contamination of 1-2.
[0035]
Milling acid dye Nylosan Blue N-GFL (manufactured by Clariant Japan Co., Ltd.)
From the above results, the fastness of fabrics made of ordinary homopolymers is excellent even with acidic dyes, but in copolymerized nylon fabrics, there is a large difference in fastness, and the present invention has a remarkable effect over copolymerized polyamides. I know that there is.
[0036]
Example 1
Nylon 6 (36 denier 17 filaments) and nylon 6 (80% by weight) copolymerized nylon (36 denier 17 filaments) in which nylon 66 is copolymerized by 20% by weight are mixed at a ratio of 1: 1 to obtain 70 denier 34 filaments. Dyed fabric 3 was obtained by dyeing and soaping the fabric obtained as a blended yarn with the following dyes. The appearance of the fabric obtained here has a novel appearance with a slight difference in light and shade, and the fastness to washing is evaluated. I understood.
[0037]
Carboxypyridiniotriazine type reactive dye Kayaceron React Blue CN-MG (Nippon Kayaku Co., Ltd.)
[0038]
Example 2
A dyed fabric 4 was obtained in the same manner as in Example 1 , except that the dyes were changed as follows. Although the appearance of the fabric obtained here is slightly smaller than the dyed fabric 3 , it has a new appearance with a gentle difference in shade and the fastness to washing was evaluated. It was found to be ˜5 grade and good fastness.
[0039]
Bromoacrylamide-type reactive dye, Lansol Blue 3G (manufactured by Ciba Specialty Chemicals)
[0040]
Comparative Example 2
Using the same fabric as in Example 1 , dyeing with the following dyes and fixing treatment were performed to obtain a dyed fabric 5 . The fabric obtained here had no fine contrast, and the fastness to washing was evaluated. As a result, it was found that the discoloration color was 3rd grade and the contamination was 2nd to 3rd grade.
[0041]
Milling acid dye Nylosan Blue N-GFL (manufactured by Clariant Japan Co., Ltd.)
From the above results, by dyeing the mixed yarn of the polyamide comprising the copolymerized polyamide and the homopolymer, the method of the present invention has a new appearance with good washing fastness and a fine gradation difference. On the other hand, it was found that the dyed dyestuffs with acid dyes have poor washing fastness and the appearance cannot obtain a fine difference in shade.
[0042]
【The invention's effect】
According to the present invention, it is possible to obtain a copolymerized polyamide fiber dyed article having a good wet fastness and exhibiting a novel appearance with a gentle difference in shade by using two or more polyamide fibers. I can do it.

Claims (6)

A composite polyamide obtained by copolymerizing at least one copolymer component of 3% by weight or more and less than 60% by weight with nylon 6 and / or nylon 66 is combined, mixed or interwoven with the main component polyamide. A polyamide fiber characterized by being dyed with a reactive dye having at least one bromoacrylamide group, monochlorotriazine group, monofluorotriazine group, carboxypyridiniotriazine group, or fluorochloropyrimidine group. Dyeing method. The method for dyeing polyamide-based fibers according to claim 1, wherein a surfactant containing nitrogen atoms tertiary and / or quaternized in the molecular structure is added to the dyeing solution. The method for dyeing polyamide-based fibers according to claim 2 , wherein the surfactant is an amphoteric surfactant. The dyeing method according to any one of claims 1 to 3 , further comprising a soaping treatment at a pH of 8 to 12 after dyeing. A polyamide fiber dyed product obtained by the dyeing method according to any one of claims 1 to 4 . A composite polyamide, nylon 6 and / or nylon 66 are combined, mixed or interwoven with at least one copolymer component of 3% by weight or more and less than 60% by weight with respect to the main component polyamide. The polyamide fiber structure is dyed with a reactive dye containing at least one bromoacrylamide group, monochlorotriazine group, monofluorotriazine group, carboxypyridiniotriazine group, or fluorochloropyrimidine group . JIS L-0844 A-2 method A polyamide fiber dyeing product characterized in that the fastness to washing as defined in 1 is grade 4 or higher and has a light and dark color.